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Decisive role of MgO addition in the ultra-broad

temperature stability of multicomponent
BaTiO3-based ceramics
ARTICLE in CERAMICS INTERNATIONAL JANUARY 2014
Impact Factor: 2.61 DOI: 10.1016/j.ceramint.2013.06.110

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CERAMICS
INTERNATIONAL

Ceramics International 40 (2014) 11051110

www.elsevier.com/locate/ceramint

Decisive role of MgO addition in the ultra-broad temperature stability of

multicomponent BaTiO3-based ceramics
Lingxia Lin, Mingjing Wang, Yaran Liu, Junxiao Chen, Ning Zhang
School of Electronic and Information Engineering, Tianjin University, Tianjin 300072, China
Received 1 May 2013; received in revised form 28 June 2013; accepted 28 June 2013
Available online 5 July 2013

Abstract
High capacitance temperature stability (the capacitance is within 7 15% of room temperature capacitance) in an ultra-broad temperature range
of
55 1C to 300 1C has been achieved by synthesizing multicomponent BaTiO3-based ceramics consisting of BaTiO3, Na0.5Bi0.5TiO3, Nb2O5,
CeO2, glass and MgO. Signicantly, MgO addition plays a decisive role in achieving the ultra-broad temperature stability and acquiring an
appropriate microstructure. Doping different amounts of MgO can alter the temperature dependence of dielectric constant markedly, especially in
a high temperature range of 200 1C300 1C. The maximum capacitance variation rate is reduced from
60% to only 10% by doping appropriate
content of MgO. In terms of the microstructure, MgO additive can suppress the formation of Ti-rich phase and sheet grains, which are detrimental
to the capacitance temperature stability. The sample with 1.5 wt% MgO has superior dielectric and electrical properties at room temperature
(r 1675, tan 1.452%, and V 5  1012 cm).
& 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Keywords: Dielectrics; Ceramics; BaTiO3; Temperature stability

1. Introduction
High and stable dielectric constants over a broad temperature
are signicant for BaTiO3-based ceramics, due to their use in
multi-layer ceramic capacitors (MLCCs). Electronic Industries
Alliance (EIA) X7R and X8R specications (X7R: from
55 to
125 1C, the capacitance is within 715% of room temperature
capacitance; X8R: from
55 to 150 1C, the capacitance is within
715% of room temperature capacitance) were established to meet
requirements for different applications [14]. However, X7R, X8R
or even X9R (from
55 to 200 1C, the capacitance is within
715% of room temperature capacitance) [59] materials cannot
satisfy the application requirements of MLCCs in harsh conditions, such as oil drilling, aerospace and automotive environment
[1013]. For example, the working temperature in the cylinder is
200300 1C [10]. So it is of great need to develop ultra-broad
temperature stable materials for a wider application. We previously reported that BaTiO3Na0.5Bi0.5TiO3Nb2O5MgO-rare
earth oxide system acquired X9R characteristics, and found that
the multicomponent BaTiO3-based system was promising for the
n

Corresponding author. Tel./fax:+86 22 27402838.

E-mail address: llxtju@126.com (L. Li).

capacitance temperature stability in an ultra-broad temperature

range of
55 1C to 300 1C [9,14]. MgO is an important additive
in BaTiO3-based ceramics, and many studies have shown that
MgO additive can help satisfy X7R and X8R specications by
promoting the coreshell structure or suppressing grain growth
[1519]. While, there is no relative investigations about the effect
of MgO on ultra-broad temperature stable ceramics, especially the
effect on the dielectric properties in a high temperature range of
200 1C300 1C.
In this study, we prepared multicomponent BaTiO3-based
ceramics to achieve the ultra-broad temperature stability (from

55 to 300 1C, the capacitance is within 7 15% of room
temperature capacitance). Furthermore, we investigated the
effects of different MgO contents on the dielectric properties
and microstructure of multicomponent BaTiO3-based ceramics, and discussed the decisive role of MgO addition in
achieving the ultra-broad temperature stability.
2. Experimental procedures
The experimental procedure of multicomponent BaTiO3based ceramics is depicted in Fig. 1. The purity of starting

0272-8842/$ - see front matter & 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
http://dx.doi.org/10.1016/j.ceramint.2013.06.110

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L. Li et al. / Ceramics International 40 (2014) 11051110

materials is higher than 99%. Na0.5Bi0.5TiO3 (NBT) powders

were synthesized by using reagent-grade oxide or carbonate
powders of Na2CO3, Bi2O3 and TiO2. The starting materials
were mixed by ball-milling for 4 h using zirconia milling
media in deionized water, followed by drying, then calcined at
800 1C to synthesize NBT. Precursor was composed of
BaTiO3 (400 nm average grain size, Guoci Co. Ltd., China),
synthesized NBT and Nb2O5 powders with the mole ratio of
BT:NBT:Nb2O5 85:15:2. The powders were mixed by ballmilling for 4 h, and then calcined at 1000 1C for 2 h. The glass
powders were synthesized by 23.55 wt% Bi2O3, 19.85 wt%
TiO2, 24.30 wt% ZnO and 32.30 wt% B2O3. In the nal
preparation of samples, 25 g precursor, 0.10 g CeO2, 1.25 g
glass powders and various amounts of MgO (0.0, 1.0, 1.5 and
2.0 wt%) were mixed by 2 h ball-milling. After drying, mixed
powders were added in 7 wt% binder wax, and then pressed
into discs with 20 mm in diameter and 1 mm in thickness.
Samples were sintered at 1130 1C for 1 h.
Dielectric loss and capacitance were measured by use of a
capacitance meter (HP4278A) at 1 kHz, with temperature
range of
55 1C to 300 1C. The capacitance variation rate
(C/C20 1C) is calculated by using the equation C/C20 1C
(C
C20 1C)/C20 1C  100%, where C20 1C is the capacitance at
20 1C, and C is the capacitance of either temperature in the
range of
55 1C to 300 1C. The frequency characteristics
were measured between 200 Hz and 1 MHz, using a TH2828S
automatic component analyzer. Insulation resistance was
measured using a high resistance meter (Agilent 4339B) at
room temperature. Crystal structure of the samples was
identied at room temperature using an X-ray diffractometer
(D8-Focus, Bruker AXS GmbH, Germany). Microstructure of
the ceramic samples was observed by eld emission scanning
electron microscopy (FE-SEM, S-4800, Hitachi, Ltd., Japan).
Element distribution of different areas was analyzed by energy
dispersive spectrometry (EDS).

Fig. 1. Flow chart for the fabrication of the multicomponent BaTiO3-based

ceramics.

3. Results and discussion

Fig. 2 shows the temperature dependence of dielectric constant
for samples with various amounts of MgO. The curve of the
sample without MgO presents an obvious dielectric constant
peak at about 125 1C, just as pure BaTiO3. For the sample with
1.0 wt% MgO, the peak at 125 1C is suppressed, and meanwhile,
the dielectric constant is markedly enhanced at lower temperature. With the continued increasing MgO content, the curve
shape changes greatly. In the case of 1.5 wt% and 2.0 wt%
MgO, there are two dielectric constant peaks at about
20 1C
and 250 1C. The change is benecial to the improvement of
temperature stability, especially in the high-temperature range
(150 1C300 1C). The effect of MgO addition on the temperature
stability of samples can be also described well by the temperature dependence of capacitance variation rate, as shown in Fig. 3.
For the sample with 0.0 wt% and 1.0 wt% MgO, the capacitance
variation rate is relatively large in the high-temperature range
(150 1C300 1C). The maximum capacitance variation rate of the
sample with 1.0 wt% MgO is even up to
60%. When MgO
doping content reaches to 1.5 wt%, the temperature stability is
improved dramatically, especially in the high-temperature range.
The maximum capacitance variation rate is down to only about
10%, which can satisfy the ultra-broad temperature stability
specication well. While, the capacitance variation rate is beyond
15% in the temperature from 200 1C to 300 1C for the sample
with 2.0 wt% MgO. Therefore, appropriate amount of MgO
addition enables BaTiO3-based ceramics to satisfy the ultrabroad temperature stability. The dielectric loss curves of different
samples over the broad temperature range of
55 C to 300 1C
are shown in Fig. 4. Dielectric loss data of samples with 1.5 wt%
and 2.0 wt% MgO differ from those of samples with 0.0 wt%
and 1.0 wt% MgO. The curves of samples with 0.0 wt% and
1.0 wt% MgO are relatively at; while, a distinct dielectric loss
peak around 200 1C is observed in the samples with 1.5 wt% and
2.0 wt% MgO. Leakage conductivity has an important effect on
dielectric loss in high temperature [6]. In our multicomponent
system, the leakage conductivity is supposed to be produced by
migration of oxygen vacancies [20]. Zhang et al. reported that

Fig. 2. Temperature dependence of dielectric constant for samples with

various amounts of MgO.

L. Li et al. / Ceramics International 40 (2014) 11051110

1107

Ca-doped BaTiO3 had higher grain conductivity at modest

temperatures compared to undoped BaTiO3 ceramics and
signicantly lower activation energies associated with the bulk
conduction mechanism, 0.40.6 eV compared to 1.40 eV for
undoped BaTiO3 [21]. Accordingly, it is speculated that the
incorporation of Mg will also have a profound effect on bulk
conduction mechanism, i.e., lowering the activation energy.

Insulation resistivity of samples with different Mg doping

contents is shown in Table 1. Insulation resistivity decreases
gradually with the increasing of Mg doping, which means that
the incorporation of Mg increase the conductivity of samples. It
is reasonable to predict that the conductivity of samples with Mg
doping will increase with increasing temperature because high
temperature will promote the motion of oxygen vacancies.

Fig. 3. Temperature dependence of capacitance variation rate based on C20 1C

for samples with various amounts of MgO.

Fig. 5. Frequency dependence of dielectric constant for samples with various

amounts of MgO.

Fig. 4. Temperature dependence of dielectric loss for samples with various

amounts of MgO.

Fig. 6. Frequency dependence of dielectric loss for samples with various

amounts of MgO.

Table 1
Dielectric and electrical properties of the samples.
MgO content (mol%)

0.0
1.0
1.5
2.0

r at 20 1C

1405
1497
1675
1753

tan at 20 1C (%)

1.354
0.743
1.452
1.929

C/C20 1C (%)

Insulation resistivity (1013 cm)

55 1C

300 1C

16.1

9.4

3.3

2.3

55.4

59.4
6.4
16.6

6.1
1.8
0.5
0.4

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L. Li et al. / Ceramics International 40 (2014) 11051110

The dependence of dielectric constant on frequency is

shown in Fig. 5. The dielectric constant increases with
increasing MgO content in the frequency range from 200 Hz
to 1 MHz. For the samples with different amounts of MgO, the
variation of dielectric constant with frequency is similar:
dielectric constant decreases gradually with increasing frequency. The higher dielectric constant at lower frequencies is
due to the contribution of all different types of polarizations
(i.e. electronic, ionic, dipolar, interfacial, etc.) [22]. While,
only electronic and ionic polarization is dominated at higher
frequencies. Fig. 6 shows the dependence of dielectric loss on
frequency. The values of samples with 0.0 wt% and 1.0 wt%
MgO increase with increasing frequency; while, the values of
samples with 1.5 wt% and 2.0 wt% MgO decrease rst and
then increase with increasing frequency.

Fig. 7. XRD patterns of samples with various amounts of MgO.

Main dielectric and electrical properties of the samples are listed

in Table 1. Dielectric constant at 20 1C increases with the increase
of MgO content. Dielectric loss at 20 1C is all lower than 2.0%.
With increasing MgO content, the dielectric loss (tan ) at 20 1C
decreases rst, and then increases. Besides, samples have superior
insulation resistivity (41012 cm), but the insulation resistivity
decreases gradually with the increasing of MgO content as
discussed above. In brief, the sample with 1.5 wt% MgO is
obtained to satisfy the ultra-broad temperature stability. Particularly, the ceiling working temperature has been greatly enhanced
from 200 1C to 300 1C. Meanwhile, it has superior dielectric and
electrical properties at room temperature: high dielectric constant
(1675), low dielectric loss (1.452%) and high insulation resistivity
(5  1012 cm).
Fig. 7 shows XRD patterns of the multicomponent BaTiO3based ceramics with different amounts of MgO. As discussed
above, the sample with 1.5 wt% MgO obtains the optimum
performance. Compared with its pattern, there is a much more
noticeable Ti-rich phase in the pattern of the sample without
MgO, such as BaO(TiO2)4. It is found that diffraction peak
intensity of the Ti-rich phase decreases perceptibly with the
increase of MgO content. In particular, the Ti-rich phase is
oblivious in the pattern of the sample with 1.5 wt% MgO.
Many studies have reported that some additives can react with
BaTiO3 to form disparate phases, such as Ba4Ti13O20,
Ba6Ti17O40 and Ba2TiSi2O8 [2325]. In our multicomponent
BaTiO3-based ceramics, the Ti-rich phase was formed via the
reaction of excess TiO2 with BaTiO3. To associate with the
dielectric properties above, the Ti-rich phase is detrimental to
the capacitance temperature stability, especially in the hightemperature range. It is an appropriate amount (1.5 wt%) of
MgO addition that suppresses the Ti-rich phase effectively and
improves the temperature stability.

Fig. 8. SEM photos of samples with various amounts of MgO: (a) 0.0 wt%; (b) 1.0 wt%; (c) 1.5 wt%; and (d) 2.0 wt%.

L. Li et al. / Ceramics International 40 (2014) 11051110

Fig. 9. Element distribution of two kinds of grains in the sample without MgO.

SEM images of samples with different amounts of MgO are

shown in Fig. 8. There are a lot of sheet grains in the sample
without MgO. However, with the increasing content of MgO,
the sheet grains reduce drastically and even disappear in the
sample with 1.5 wt% and 2.0 wt% MgO. To conrm the
element distribution in different grains, EDS analysis was
carried out and the result is given in Fig. 9. In normal grains,
Ti/Ba ratio is about 1. While, in sheet grains, Ti/Ba ratio is
approximately 3. It can be considered that the sheet grains are
mainly consisting of the Ti-rich phase, as mentioned in the
discussion of XRD patterns. The results t well with the
change in XRD patterns. Likewise, sheet grains are detrimental
to the ultra-broad temperature stability, and appropriate MgO
content can suppress the formation of sheet grains effectively.

4. Conclusions
Multicomponent BaTiO3-based ceramics consisting of
BaTiO3, Na0.5Bi0.5TiO3, Nb2O5, CeO2, glass and MgO were
synthetized and investigated. In the system, MgO addition
plays a decisive role in achieving the ultra-broad temperature
stability and acquiring an appropriate microstructure. MgO
additive can alter the curve shape of temperature dependence
of dielectric constant greatly: from curves with one dielectric
peak at 1251C to curves with two dielectric peaks at
20 1C
and 250 1C. Capacitance temperature stability is improved
effectively: maximum capacitance variation rate is reduced
from
60% to only 10%. Sample with 1.5 wt% MgO has the
optimum performance: the capacitance variation rate based on
C20 1C is within 7 15% in the ultra-broad temperature range of

55 1C to 300 1C; meanwhile, it maintains good dielectric
and electrical properties at room temperature-high dielectric
constant (1675), low dielectric loss (1.452%) and high insulation resistivity (5  1012 cm). Ti-rich phase and sheet grains,
which are detrimental to the capacitance temperature stability,
reduce dramatically with the increasing content of MgO.

References
[1] L. Li, R. Fu, Q. Liao, L. Ji, Doping behaviors of NiO and Nb2O5 in
BaTiO3 and dielectric properties of BaTiO3-based X7R ceramics,
Ceramics International 38 (2012) 19151920.

1109

[2] Y. Sun, H. Liu, H. Hao, S. Zhang, L. Guo, Z. Yu, Effect of

Na0.5Bi0.5TiO3 on dielectric properties of BaTiO3 based ceramics,
Ceramics International 38 (2012) S41S44.
[3] L. Li, M. Wang, D. Guo, R. Fu, Q. Meng, Effect of Gd amphoteric
substitution on structure and dielectric properties of BaTiO3-based
ceramics, Journal of Electroceramics 30 (2013) 129132.
[4] J. Kim, T. Noh, S. Jeon, S. Park, H. Chun, H. Lee, Deterioration behavior
analysis of dysprosium and thulium co-doped barium titanate ceramics
for multilayer ceramic capacitors, Ceramics International 38 (2012)
68376842.
[5] S. Wang, J. Li, Y. Hsu, Y. Wu, Y. Lai, M. Chen, Dielectric properties and
microstructures of non-reducible high-temperature stable X9R ceramics,
Journal of the European Ceramic Society 33 (2013) 17931799.
[6] G. Yao, X. Wang, Y. Zhang, Z. Shen, L. Li, Nb-modied 0.9BaTiO30.1
(Bi0.5Na0.5)TiO3 ceramics for X9R high-temperature dielectrics application prepared by coating method, Journal of the American Ceramic
Society 95 (2012) 35253531.
[7] B. Tang, S. Zhang, X. Zhou, Y. Yuan, L. Yang, Preparation and
modication of high Curie point BaTiO3-based X9R ceramics, Journal
of Electroceramics 25 (2010) 9397.
[8] S. Gao, S. Wu, Y. Zhang, H. Yang, X. Wang, Study on the microstructure
and dielectric properties of X9R ceramics based on BaTiO3, Materials
Science and Engineeing B: Advanced Functional Solid-State Materials 176
(2011) 6871.
[9] L. Li, Y. Han, P. Zhang, C. Ming, X. Wei, Synthesis and characterization
of BaTiO3-based X9R ceramics, Journal of Materials Science 44 (2009)
55635568.
[10] R.W. Johnson, J.L. Evans, P. Jacobsen, J.R. Thompson, M. Christopher,
The changing automotive environment: high-temperature electronics,
IEEE Transactions on Electronics Packaging Manufacturing 27 (2004)
164176.
[11] M.R. Werner, W.R. Fahrner, Review on materials, microsensors, systems
and devices for high-temperature and harsh-environment applications,
Industrial Electronics, IEEE Transactions on Industrial Electronics 48
(2001) 249257.
[12] Y. Yuan, C.J. Zhao, X.H. Zhou, B. Tang, S.R. Zhang, High-temperature
stable dielectrics in Mn-modied (1
x)Bi0.5Na0.5TiO3xCaTiO3 ceramics, Journal of Electroceramics 25 (2010) 212217.
[13] J.B. Lim, S. Zhang, N. Kim, T.R. Shrout, High-temperature dielectrics in
the BiScO3BaTiO3(K1/2Bi1/2)TiO3 ternary system, Journal of the
American Ceramic Society 92 (2009) 679682.
[14] L. Li, D. Guo, W. Xia, Q. Liao, Y. Han, Y. Peng, An ultra-broad working
temperature dielectric material of BaTiO3-based ceramics with Nd2O3
addition, Journal of the American Ceramic Society 95 (2012) 21072109.
[15] J.H. Hwang, S.K. Choi, Y.H. Han, Dielectric properties of BaTiO3
codoped with Er2O3 and MgO, Japanese Journal of Applied Physics 40
(2001) 4952.
[16] S. Wang, S. Zhang, X. Zhou, B. Li, Z. Chen, Inuence of
sintering atmosphere on the microstructure and electrical properties of
BaTiO3-based X8R materials, Journal of Materials Science 41 (2006)
18131817.
[17] S.H. Yoon, J.H. Lee, D.Y. Kim, N.M. Hwang, Effect of the liquid-phase
characteristic on the microstructures and dielectric properties of donor(niobium) and acceptor-(magnesium) doped barium titanate, Journal of
the American Ceramic Society 86 (2003) 8892.
[18] J.S. Park, M.H. Yang, Y.H. Han, Effects of MgO coating on the sintering
behavior and dielectric properties of BaTiO3, Materials Chemistry and
Physics 104 (2007) 261266.
[19] J.S. Park, Y.H. Han, Effects of MgO coating on microstructure and
dielectric properties of BaTiO3, Journal of the European Ceramic Society
27 (2007) 10771082.
[20] Y. Li, X. Yao, L. Zhang, Dielectric properties and microstructure of
magnesium-doped Ba1+k(Ti1
xCax)O3
x+k ceramics, Ceramics International 30 (2004) 12831287.
[21] L. Zhang, O.P. Thakur, A. Feteira, G.M. Keith, A.G. Mould, D.
C. Sinclair, A.R. West, Comment on the use of calcium as a dopant
in X8R BaTiO3-based ceramics, Applied Physics Letters 90 (2007)
142914.

1110

L. Li et al. / Ceramics International 40 (2014) 11051110

[22] H. Wu, Y. Pu, Z. Wang, K. Chen, Study of electrical and dielectric

properties of Y2O3 doped Ba1
x(Bi0.5Na0.5)xTiO3 ceramics, Materials
Letters 76 (2012) 222225.
[23] P. Bomlai, N. Sirikulrat, T. Tunkasiri, Effect of heating rate on the
properties of Sb and Mn-doped barium strontium titanate PTCR ceramics,
Materials Letters 59 (2005) 118122.

[24] T. Bin, Z. Shu-Ren, Z. Xiao-Hua, Effect of Mn2+ doping on the

temperature coefcient of capacitance of TiO2/SiO2-doped BaTiO3
ceramics, Inorganic Materials 44 (2008) 669672.
[25] D. Vltzke, H. Abicht, Mechanistic investigations on the densication
behaviour of barium titanate ceramics, Solid State Sciences 3 (2001)
417422.